EP3352282A1 - Batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage de puissance et système de puissance - Google Patents

Batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage de puissance et système de puissance Download PDF

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Publication number
EP3352282A1
EP3352282A1 EP16853223.2A EP16853223A EP3352282A1 EP 3352282 A1 EP3352282 A1 EP 3352282A1 EP 16853223 A EP16853223 A EP 16853223A EP 3352282 A1 EP3352282 A1 EP 3352282A1
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EP
European Patent Office
Prior art keywords
battery
present
negative electrode
positive electrode
electrolytic solution
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Pending
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EP16853223.2A
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German (de)
English (en)
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EP3352282A4 (fr
Inventor
Toru Odani
Tadahiko Kubota
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Murata Manufacturing Co Ltd
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Tohoku Murata Manufacturing Co Ltd
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Application filed by Tohoku Murata Manufacturing Co Ltd filed Critical Tohoku Murata Manufacturing Co Ltd
Publication of EP3352282A1 publication Critical patent/EP3352282A1/fr
Publication of EP3352282A4 publication Critical patent/EP3352282A4/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • H—ELECTRICITY
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    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
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    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present technology relates to a battery, a battery pack, an electronic device, an electric vehicle, an electric storage device, and an electric power system.
  • Recent electronic devices and the like tend to have higher performance and multifunctionality more and more.
  • Various configurations are adopted in order to improve characteristics of batteries applied to electronic devices and the like.
  • Patent Document 1 For example, in order to improve safety of batteries, improvements have been made by disposing insulating materials such as alumina in layers between positive and negative electrodes of the battery.
  • Patent Document 2 For example, in order to improve safety of batteries, improvements have been made by disposing insulating materials such as alumina in layers between positive and negative electrodes of the battery.
  • Patent Document 3 describe that characteristics are improved by adding an additive to an electrolytic solution.
  • the present technology is a battery including an electrode group including a positive electrode and a negative electrode, and an electrolyte including an electrolytic solution, wherein the electrode group includes an insulating layer having an insulating material, and the electrolytic solution contains a nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more and an additive composed of at least one of the compounds represented by a formula (1) to a formula (2).
  • R1 and R2 each independently represent a hydrogen group, an alkyl group, an alkenyl group or an alkynyl group optionally having a substituent and having 1 to 4 carbon atoms
  • n is an integer of 1 to 3
  • M is a metal ion.
  • R3, R4 and R5 each independently represent a hydrogen group, an alkyl group, an alkenyl group or an alkynyl group optionally having a substituent and having 1 to 4 carbon atoms.
  • the present technology is a battery including an electrode group including a positive electrode and a negative electrode, and an electrolyte including an electrolytic solution, a polymer compound which holds the electrolytic solution and an insulating material, wherein the electrolytic solution contains a nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more and an additive composed of at least one of the compounds represented by a formula (1) to a formula (2).
  • the battery pack, the electronic device, the electric vehicle, the electric storage device, and the electric power system of the present technology are provided with the above-mentioned battery.
  • the battery of the present technology it is possible to improve high-temperature cycle characteristics by having an insulating layer and using a predetermined electrolytic solution. Similar effects can be achieved in the battery pack, the electronic device, the electric vehicle, the electric storage device, and the electric power system of the present technology using the above battery.
  • nonaqueous electrolyte battery a cylindrical nonaqueous electrolyte secondary battery (hereinafter, referred to as “nonaqueous electrolyte battery” or simply “battery”) will be described with reference to FIG. 1 and FIG. 2 as an example.
  • the nonaqueous electrolyte battery mainly includes a wound electrode body 20 and a pair of insulating plates 12, 13 housed in a substantially hollow cylindrical battery can 11.
  • a battery structure using such a battery can 11 is called a cylindrical type.
  • the battery can 11 has, for example, a hollow structure in which one end portion is closed and the other end portion is open, and is made of iron (Fe), aluminum (Al), an alloy thereof, or the like.
  • the battery can 11 is made of iron, for example, nickel (Ni) or the like may be plated on the surface of the battery can 11.
  • the pair of insulating plates 12, 13 sandwich the wound electrode body 20 from above and below and are disposed so as to extend perpendicularly to the peripheral surface of the wound electrode body.
  • a battery cover 14, a safety valve mechanism 15, and a positive temperature coefficient element (PTC element) 16 are crimped at the open end of the battery can 11 with a gasket 17 interposed among them, and the battery can 11 is hermetically sealed.
  • the battery cover 14 is made of, for example, the same material as the battery can 11.
  • the safety valve mechanism 15 and the positive temperature coefficient element 16 are provided inside the battery cover 14.
  • the safety valve mechanism 15 is electrically connected to the battery cover 14 with the positive temperature coefficient element 16 interposed therebetween.
  • a disk plate 15A is configured to be reversed to cut electrical connection between the battery cover 14 and the wound electrode body 20.
  • the positive temperature coefficient element 16 prevents abnormal heat generation due to a large current by increasing the resistance (by limiting the current) according to the increase in temperature.
  • the gasket 17 is made of, for example, an insulating material, and, for example, asphalt is applied onto the surface of the gasket 17.
  • the wound electrode body 20 is an electrode group in which a positive electrode 21 and a negative electrode 22 are laminated and wound with a separator 23 interposed therebetween.
  • a center pin 24 may be inserted in the center of the wound electrode body 20.
  • a positive electrode lead 25 is connected to the positive electrode 21 of the wound electrode body 20 and a negative electrode lead 26 is connected to the negative electrode 22.
  • the positive electrode lead 25 is welded to the safety valve mechanism 15 to be electrically connected to the battery cover 14, and the negative electrode lead 26 is welded to the battery can 11 to be electrically connected to the battery can 11.
  • the positive electrode lead 25 is, for example, a thin plate-shaped conductive member, and is made of, for example, aluminum or the like.
  • the negative electrode lead 26 is, for example, a thin plate-shaped conductive member and is made of copper (Cu), nickel, stainless steel (SUS) or the like.
  • the positive electrode 21 is, for example, one in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A.
  • the positive electrode 21 may have a region in which the positive electrode active material layer 21B is provided only on one surface of the positive electrode current collector 21A.
  • a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil can be used.
  • the positive electrode active material layer 21B contains a positive electrode active material.
  • the positive electrode active material layer 21B may contain other materials such as a conductive agent and a binder, as required.
  • the positive electrode active material for example, a material capable of absorbing and releasing lithium can be used.
  • a lithium-containing compound can be used.
  • lithium-containing compound examples include a composite oxide containing lithium and a transition metal element (referred to as “lithium transition metal composite oxide”), a phosphate compound containing lithium and a transition metal element (“lithium transition metal phosphate compound”) and the like.
  • lithium transition metal composite oxide a composite oxide containing lithium and a transition metal element
  • lithium transition metal phosphate compound a phosphate compound containing lithium and a transition metal element
  • the lithium-containing compound those containing at least one of cobalt (Co), nickel, manganese (Mn), and iron as transition metal elements are preferred. The reason for this is that a higher voltage can be attained.
  • lithium transition metal composite oxide examples include a lithium transition metal composite oxide having a layered rock salt structure, and a lithium transition metal composite oxide having a spinel structure.
  • lithium transition metal composite oxide having a layered rock salt structure examples include lithium-containing compounds represented by the general formula Li x M1O 2 (in the formula, M1 represents an element including one or more transition metal elements, the value of x is 0.05 ⁇ x ⁇ 1.10 as an example, and the value of x varies depending on a charge-discharge state of the battery and is not limited thereto), and the like.
  • More specific examples include a lithium cobalt composite oxide (Li x CoO 2 ), a lithium nickel composite oxide (Li x NiO 2 ), a lithium nickel cobalt composite oxide (Li x Ni 1-z Co z O 2 (0 ⁇ z ⁇ 1)), a lithium nickel cobalt manganese composite (Li x Ni (1-v-w) Co v Mn w O 2 (0 ⁇ v + w ⁇ 1, v > 0, w > 0)), a lithium cobalt aluminum magnesium composite oxide (Li x CO (1-p-q) Al p Mg q O 2 (0 ⁇ p + q ⁇ 1, p > 0, q > 0)), and the like.
  • lithium transition metal composite oxide having a spinel structure examples include lithium manganese composite oxide (LiMn 2 O 4 ), lithium manganese nickel composite oxide (Li x Mn 2-t Ni t O 4 (0 ⁇ t ⁇ 2)), and the like.
  • lithium transition metal phosphate compound examples include a lithium transition metal phosphate compound having an olivine structure and the like.
  • lithium transition metal phosphate compound having an olivine structure examples include lithium-containing compounds represented by the general formula Li y M2PO 4 (in the formula, M2 represents an element including one or more transition metal elements, the value of y is 0.05 ⁇ y ⁇ 1.10 as an example, and the value of y varies depending on a charge-discharge state of the battery and is not limited to this range), and the like. More specific examples include a lithium iron phosphate compound (Li y FePO 4 ), a lithium iron manganese phosphate compound (Li y Fe 1-u Mn u PO 4 (0 ⁇ u ⁇ 1)), and the like.
  • Li y M2PO 4 in the formula, M2 represents an element including one or more transition metal elements, the value of y is 0.05 ⁇ y ⁇ 1.10 as an example, and the value of y varies depending on a charge-discharge state of the battery and is not limited to this range
  • More specific examples include a lithium iron phosphate compound (Li
  • Coated particles having particles of the above-mentioned lithium-containing compound and a coating layer provided on at least a part of the surface of the particles of the lithium-containing compound may be used as the positive electrode active material. By using such coated particles, battery characteristics can be more improved.
  • the coating layer is provided on at least a part of the surface of the particle (base material particle) of the lithium-containing compound to be the base material, and has a composition element or composition ratio different from that of the base material particle.
  • a material of the covering layer include those containing an oxide, a transition metal compound or the like.
  • Specific examples of the material of the coating layer include oxides containing lithium and at least one of nickel and manganese, and compounds containing at least one selected from the group consisting of nickel, cobalt, manganese, iron, aluminum, magnesium (Mg), and zinc (Zn), oxygen (O) and phosphorus (P), and the like.
  • the coating layer may contain a halide such as lithium fluoride or a chalcogenide other than oxygen.
  • the presence of the coating layer can be confirmed by examining the concentration change of the constituent elements from the surface of the positive electrode active material to the inside.
  • the concentration change can be obtained by scraping particles of the lithium-containing compound provided with the coating layer by sputtering or the like and measuring the composition thereof by Auger Electron Spectroscopy (AES) or Secondary Ion Mass Spectrometry (SIMS)). It is also possible to dissolve the particles of the lithium-containing compound provided with the coating layer slowly in an acidic solution or the like and to measure the time change of the elution by inductively coupled plasma (ICP) spectroscopy or the like.
  • ICP inductively coupled plasma
  • an oxide, a disulfide, a chalcogenide not containing lithium in particular, a layered compound or a spinel type compound
  • a conductive polymer or the like can be used as the positive electrode active material.
  • the oxide include vanadium oxide (V 2 O 5 ), titanium dioxide (TiO 2 ), manganese dioxide (MnO 2 ), and the like.
  • the disulfide include iron disulfide (FeS 2 ), titanium disulfide (TiS 2 ), molybdenum disulfide (MoS 2 ), and the like.
  • the chalcogenide not containing lithium include niobium diselenide (NbSe 2 ) and the like.
  • the conductive polymer include sulfur, polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.
  • the positive electrode active material may be other than the positive electrode active material exemplified above.
  • two or more kinds of positive electrode active materials exemplified above may be a mixture of two or more thereof in arbitrary combination.
  • a conductive agent for example, a carbon material or the like can be used.
  • the carbon material include graphite, carbon black, acetylene black, and the like.
  • the conductive agent may be a metal material, a conductive polymer or the like as long as it is a conductive material.
  • the binder for example, a resin material or the like can be used.
  • the resin material include polyvinylidene fluoride (PVdF), polyamide imide (PAI), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene-butadiene rubber (SBR) or carboxymethyl cellulose (CMC).
  • the negative electrode 22 has a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A.
  • the negative electrode 22 may have a region where the negative electrode active material layer 22B is provided only on one surface of the negative electrode current collector 22A.
  • the negative electrode current collector 22A for example, a metal foil such as a copper foil can be used.
  • the negative electrode active material layer 22B contains a negative electrode active material.
  • the negative electrode active material layer 22B may contain other materials such as a conductive agent and a binder, as required.
  • the conductive agent and the binder the same materials as the conductive agent and the binder of the positive electrode 21 can be used.
  • the negative electrode active material for example, a material capable of absorbing and releasing lithium can be used.
  • a carbon material can be used as the negative electrode active material. In the carbon materials, changes in crystal structure generated at the time of charging and discharging are very small, a high charge-discharge capacity can be obtained, and good cycle characteristics can be attained.
  • the carbon material is, for example, graphitizable carbon, non-graphitizable carbon having a (002) plane spacing of 0.37 nm or more, or graphite having a (002) plane spacing of 0.34 nm or less. More specifically, pyrolytic carbons, cokes, glassy carbon fibers, baked organic polymer compounds, activated carbon or carbon blacks and the like are used. Of these, the cokes include pitch coke, needle coke, petroleum coke, and the like.
  • the baked organic polymer compound is one in which a polymer compound such as a phenol resin or a furan resin is baked (carbonized) at an appropriate temperature.
  • the carbon material may be low crystalline carbon heat-treated at about 1000°C or lower or amorphous carbon. A shape of the carbon material may be fibrous, spherical, granular or scaly.
  • the negative electrode active material for example, a material capable of absorbing and releasing lithium and containing at least one of a metal element and a metalloid element as a constituent element (referred to as "metal-based material") can be used.
  • the metal-based material may be, for example, a simple substance, an alloy or a compound, or a mixture of two or more thereof. When the metal-based material is used, it is preferred because a high energy density can be attained.
  • the alloy includes not only alloys composed of two or more kinds of metal elements but also alloys containing one or more kinds of metal elements and one or more kinds of metalloid elements. Also, the alloy may contain a nonmetallic element. In some alloys, a solid solution, a eutectic alloy (eutectic mixture), an intermetallic compound, or two or more kinds of them coexist in the composition thereof.
  • metal element or metalloid element for example, a metal element or a metalloid element capable of forming an alloy with lithium can be mentioned.
  • the metal element or metalloid element include magnesium, boron (B), aluminum, titanium (Ti), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) or platinum (Pt). These elements may be crystalline or amorphous.
  • the metal-based material one containing a metal element or a metalloid element of group-IVB in the short period type periodic table as a constituent element is preferred.
  • a material containing at least one of silicon and tin as a constituent element referred to as "material containing at least one of silicon and tin”
  • a material containing at least silicon referred to as “material containing silicon”
  • Silicon and tin have a large ability to absorb and release lithium, and can obtain high energy density.
  • Examples of the material containing at least one of silicon and tin include a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, a material at least partially having one or more phases thereof, or the like.
  • Examples of the alloy of silicon include alloys containing, as a second constituent element other than silicon, at least one of the group consisting of tin, nickel, copper (Cu), iron, cobalt (Co), manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb), and chromium (Cr).
  • Examples of the alloy of tin include alloys containing, as a second constituent element other than tin, at least one of the group consisting of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium.
  • the compound of tin or the compound of silicon for example, one containing oxygen or carbon (C) is mentioned, and in addition to tin or silicon, the above-mentioned second constituent element may be contained.
  • the material containing tin is preferably a SnCoC-containing material in which cobalt, tin, and carbon are contained as constituent elements, the content of carbon is 9.9% by mass or more and 29.7% by mass or less, and the ratio of cobalt to the total of tin and cobalt is 30% by mass or more and 70% by mass or less.
  • the reason for this is that a high energy density can be obtained in such a composition range and excellent cycle characteristics can be attained.
  • the SnCoC-containing material may further contain other constituent elements as necessary.
  • the other constituent elements for example, silicon, iron, nickel, chromium, indium, niobium (Nb), germanium, titanium, molybdenum (Mo), aluminum, phosphorus, gallium and bismuth are preferred, and two or more kinds thereof may be contained. The reason for this is that the capacity or cycle characteristics can be further improved.
  • the SnCoC-containing material has a phase containing tin, cobalt, and carbon, and the phase preferably has a low crystalline or amorphous structure.
  • the SnCoC-containing material it is preferred that at least a part of carbon as the constituent element is bonded to a metal element or a metalloid element which is another constituent element. The reason for this is that deterioration of cycle characteristics is thought to be due to aggregation or crystallization of tin and the like, and such aggregation or crystallization can be suppressed when carbon is bonded to other elements.
  • XPS X-ray photoelectron spectroscopy
  • a peak of C1s is used for correction of the energy axis of the spectrum.
  • the peak of C1s of surface contaminated carbon is set to 284.8 eV, which is taken as the energy reference.
  • the waveform of the peak of C1s is obtained in a form including the peak of the surface contaminated carbon and the peak of the carbon in the SnCoC-containing material. Therefore, by analysis using, for example, commercially available software, surface contaminated carbon peak is separated from the carbon peak in the SnCoC-containing material.
  • a position of a main peak present on the lowest bound energy side is defined as the energy reference (284.8 eV) .
  • the negative electrode active material for example, a metal oxide or a polymer compound capable of absorbing and releasing lithium can be used.
  • the metal oxide include lithium titanium oxide containing titanium and lithium such as lithium titanate (Li 4 Ti 5 O 12 ), iron oxide, ruthenium oxide, molybdenum oxide, and the like.
  • the polymer compound include polyacetylene, polyaniline, polypyrrole, and the like.
  • a metal containing lithium may be used as the negative electrode active material.
  • the metal containing lithium include lithium metal, an alloy containing lithium, and the like.
  • the negative electrode active material layer 22B may be made of the metal containing lithium.
  • the negative electrode active material may be other than the above.
  • two or more kinds of positive electrode active materials exemplified above may be mixed in arbitrary combination.
  • the negative electrode active material layer 22B may be formed by using, for example, a gas phase method, a liquid phase method, a thermal spraying method, a coating method, a firing method, or a method of two or more of them.
  • Examples of the gas phase method include, for example, a physical deposition method or a chemical deposition method, specifically, a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a thermal chemical vapor deposition (CVD) method or a plasma chemical vapor deposition method.
  • a liquid phase method a publicly known method such as electrolytic plating or electroless plating can be used.
  • the coating method is, for example, a method in which a particulate negative electrode active material is mixed with a binder or the like and then dispersed in a solvent for coating.
  • the firing method is, for example, a method of applying heat treatment at a temperature higher than the melting point of a binder or the like after coating by a coating method.
  • a firing method a publicly known method can be used, and, for example, an atmosphere firing method, a reaction firing method, and a hot press firing method can be mentioned.
  • the separator 23 separates the positive electrode 21 and the negative electrode 22, and allows lithium ions to pass while preventing a short circuit of the current caused by contact between both electrodes.
  • the separator 23 is, for example, a porous membrane containing a resin.
  • the porous membrane containing the resin can be obtained, for example, by forming a resin material by a stretch-opening method, a phase separation method or the like.
  • the method for producing the porous membrane containing the resin is not limited to these methods.
  • a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, a nylon resin or the like can be used.
  • the separator 23 may have a structure in which two or more porous membranes containing a resin are laminated.
  • the porous membrane containing a resin may be a mixture of two or more kinds of resin materials (one formed by melt-kneading two or more kinds of resin materials).
  • a porous membrane containing a polyolefin resin is preferred since it is excellent in separability between the positive electrode 21 and the negative electrode 22 and can more reduce the occurrence of internal short-circuit.
  • the separator 23 may be a nonwoven fabric.
  • the nonwoven fabric is a structure in which fibers are joined or entangled, or joined and entangled, without weaving or knitting fibers. Most materials that can be processed into fibers can be used as a raw material of the nonwoven fabric, and by adjusting the shape such as fiber length and thickness, it is possible to impart the function according to the purpose and use.
  • an air permeable membrane polyethylene terephthalate nonwoven fabric
  • PET polyethylene terephthalate
  • the air permeable membrane is a membrane having air permeability.
  • examples of the nonwoven fabric include nonwoven fabrics using aramid fiber, glass fiber, cellulose fiber, polyolefin fiber, nylon fiber, or the like.
  • the nonwoven fabric may use two or more kinds of fibers.
  • the battery of the present technology has a layer containing an insulating material (hereinafter, referred to as "insulating layer") disposed between the positive electrode 21 and the negative electrode 22.
  • the insulating layer is contained in the wound electrode body 20 which is an electrode group, and the insulating layer is formed, for example, between the separator 23 and the positive electrode 21, between the separator 23 and the negative electrode 22, or both of them.
  • the insulating layer may be formed by applying onto at least one side of both surfaces of the separator 23 or by applying onto at least one side of both surfaces of the positive electrode 21 or by applying onto at least one surface of both surfaces of the negative electrode 22.
  • both of the insulating layer and the separator 23 may be referred to as a separator in some cases.
  • the insulating layer is, for example, a porous layer containing a resin material and insulating particles.
  • the resin material may have a three-dimensional network structure in which fibrils are formed and fibrils are continuously connected to each other.
  • the insulating particles for example, inorganic particles or the like can be used.
  • the inorganic particles include particles of metal oxides, metal oxide hydrates, metal hydroxides, metal nitrides, metal carbides, metal sulfides, and minerals which are electrically insulating inorganic particles.
  • metal oxide or metal oxide hydrate examples include aluminum oxide (alumina, Al 2 O 3 ), boehmite (Al 2 O 3 •H 2 O or AlOOH), magnesium oxide (magnesia, MgO), titanium oxide (titania, TiO 2 ), zirconium oxide, ZrO 2 ), silicon oxide (silica, SiO 2 ), yttrium oxide (yttria, Y 2 O 3 ), zinc oxide (ZnO), and the like.
  • Examples of the metal nitride include silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN), titanium nitride (TiN), and the like.
  • Examples of the metal carbide include silicon carbide (SiC), boron carbide (B 4 C), and the like.
  • Examples of the metal sulfide include barium sulfate (BaSO 4 ) and the like.
  • Examples of the metal hydroxide include aluminum hydroxide (Al(OH) 3 ), and the like.
  • Examples of the minerals include porous aluminosilicates such as zeolite (M 2/n O•Al 2 O 3 •xSiO 2 •yH 2 O, M is a metal element, x ⁇ 2, y ⁇ 0), layered silicate such as talc (Mg 3 Si 4 O 10 (OH) 2 ), barium titanate (BaTiO 3 ), strontium titanate (SrTiO 3 ), and the like.
  • Examples of the other inorganic particles include particles of a lithium compound and particles of a carbon material.
  • Examples of the lithium compound include Li 2 O 4 , Li 3 PO 4 , LiF, and the like.
  • Examples of the carbon material include diamond and the like.
  • inorganic particles may be used singly or may be used in combination of two or more kinds thereof.
  • a shape of the inorganic particle is not particularly limited, and may be spherical, fibrous, needle-like, scaly or plate-like.
  • fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene
  • fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymers and propylene-tetrafluoroethylene copolymers
  • rubbers such as styrene-butadiene copolymers and hydrogenated products thereof, acrylonitrile-butadiene copolymers and hydrogenated products thereof, acrylonitrile-butadiene-styrene copolymers and hydrogenated products thereof, methacrylic acid ester-acrylic acid ester copolymers, styrene-acrylic acid ester copolymers, acrylonitrile -acrylic acid ester copolymers, ethylene propylene rubbers, polyvinyl alcohol, and polyvinyl acetate; cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and carboxy
  • the separator 23 is impregnated with an electrolytic solution which is a liquid electrolyte.
  • the electrolytic solution is, for example, a nonaqueous electrolytic solution containing an electrolyte salt and a nonaqueous solvent in which the electrolyte salt is dissolved.
  • the nonaqueous electrolytic solution contains 5% by mass or more of propylene carbonate as a nonaqueous solvent and contains at least one compound represented by the formula (1) and the formula (2).
  • high-temperature cycle characteristics are deteriorated also depending on the type of additive added.
  • high-temperature cycle characteristics can be improved by having an insulating layer and by using an electrolytic solution which contains a nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and at least one of the compounds represented by the formula (1) and the formula (2).
  • R1 and R2 each independently represent a hydrogen group, an alkyl group, an alkenyl group or an alkynyl group optionally having a substituent and having 1 to 4 carbon atoms
  • n is an integer of 1 to 3
  • M is a metal ion.
  • R3, R4 and R5 each independently represent a hydrogen group, an alkyl group, an alkenyl group or an alkynyl group optionally having a substituent and having 1 to 4 carbon atoms.
  • substituent means that it does not have a substituent or that a hydrogen group is substituted with one or more substituents.
  • substituents include a hydrocarbon group, a halogen group such as a fluorine group, and the like.
  • each of R1 and R2 is preferably a hydrogen group or a hydrocarbon group rather than an isopropyl group or an n-butyl group.
  • Examples of the type of the metal ion M in the formula (1) include Li + , Na + , K + , Ca 2+ , and the like.
  • examples of R5 include CH 3 -, H-, and the like.
  • M n+ Li +
  • M n+ Na +
  • M n+ K +
  • R5 CH 3
  • M n+ Ca 2+
  • R5 H
  • the addition amount of at least one of the compounds represented by formula (1) and formula (2) is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 3% by mass or less from the viewpoint of achieving a more excellent effect.
  • Examples of the compound represented by the formula (1) include compounds represented by a formula (1-1) to a formula (1-5).
  • Examples of the compound represented by the formula (2) include compounds represented by a formula (2-1) to a formula (2-8).
  • the nonaqueous solvent one containing propylene carbonate in an amount of 5% by mass or more with respect to the whole nonaqueous solvent is used.
  • the content of propylene carbonate is less than 5% by mass, the effect of improving high-temperature cycle characteristics is low even though at least one of the compounds represented by the formula (1) and the formula (2) is added as an additive.
  • the propylene carbonate has a property of hardly solidifying at a low temperature and has the merit that battery characteristics such as cycle characteristics at low temperature can be improved by containing propylene carbonate in an amount of 5% by mass or more.
  • the nonaqueous solvent may contain at least one of cyclic carbonic acid ester other than propylene carbonate, chain carbonic acid ester, chain carboxylic acid ester and cyclic carboxylic acid ester together with propylene carbonate.
  • Examples of other cyclic carbonic acid esters include ethylene carbonate, butylene carbonate, and the like.
  • chain carbonic acid esters include ethyl methyl carbonate, dimethyl carbonate, methyl propyl carbonate, diethyl carbonate, and the like.
  • Examples of the chain carboxylic acid esters include ethyl propionate, propyl propionate, and the like.
  • Examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone, and the like.
  • the electrolytic solution may contain additives other than the compounds represented by the formula (1) to the formula (2), as required.
  • Examples of other additives include dinitrile compounds, sultone (cyclic sulfonic acid ester), chain sulfonic acid ester, cyclic ether, and the like.
  • Examples of the dinitrile compound include succinonitrile, adiponitrile, and the like.
  • Examples of sultone include propane sultone, propene sultone, and the like.
  • As the chain sulfonic acid ester for example, 2-propynyl methanesulfonate and the like can be mentioned.
  • As the cyclic ether 1,3-dioxane and the like can be mentioned.
  • cyclic halogenated carbonic acid ester examples include 4-fluoro-1,3-dioxolan-2-one (FEC), 4-chloro-1,3-dioxolan-2-one, 4,5-difluoro-1,3-dioxolan-2-one (DFEC), tetrafluoro-1,3-dioxolan-2-one, 4-chloro-5-fluoro-1,3-dioxolan-2-one, 4,5-dichloro-1, 3-oxolan-2-one, tetrachloro-1,3-dioxolan-2-one, 4,5-bistrifluoromethyl-1,3-dioxolan-2-one, 4-trifluoromethyl-1,3-dioxolan-2-one, 4,5-difluoro-4,5-dimethyl-1
  • the electrolyte salt includes, for example, any one type or two or more types of lithium salt and the like described below, for example.
  • the electrolyte salt may include, for example, another salt (for example, light metal salt other than the lithium salt) other than the lithium salt.
  • Examples of the electrolyte salt as the lithium salt include lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ), Lithium methanesulfonate (LiCH 3 SO 3 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium tetrachloroaluminate (LiAlCl 4 ), dilithium hexafluorosilicate (Li 2 SiF 6 ), lithium chloride (LiCl), lithium bromide (LiBr), and the like.
  • LiPF 6 lithium hexafluorophosphate
  • LiClO 4 lithium perchlorate
  • LiAsF 6 lithium hexafluoroarsenate
  • LiB(C 6 H 5 ) 4 lithium
  • the electrolyte salt preferably contains one type or two or more types of lithium hexafluorophosphate, lithium perchlorate and lithium hexafluoroarsenate, and it more preferably contains lithium hexafluorophosphate.
  • the reason for this is that internal resistance is lowered, and a higher effect can be achieved.
  • the electrolyte salt may contain one kind or two or more kinds of other metal salts such as the lithium salt described below together with the above-mentioned lithium salt.
  • these metal salts may not be contained in the electrolyte salt together with the above-mentioned lithium salt, and may be contained alone.
  • the electrolyte salt preferably includes, as other metal salts, at least any of lithium tetrafluoroborate (LiBF 4 ), lithium difluorophosphate (LiPF 2 O 2 ), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(fluoromethanesulfonyl)imide (LiFSA), lithium monofluorophosphate (Li 2 PFO 3 ), and llithium difluoro(oxalato)borate (LiDFOB).
  • LiBF 4 lithium tetrafluoroborate
  • LiPF 2 O 2 lithium bis(oxalato)borate
  • LiTFSA lithium bis(trifluoromethanesulfonyl)imide
  • LiFSA lithium bis(fluoromethanesulfonyl)imide
  • Li 2 PFO 3 lithium monofluorophosphate
  • LiDFOB l
  • lithium ions are released from the positive electrode 21 during charging, and are absorbed in the negative electrode 22 through the electrolytic solution with which the separator 23 is impregnated.
  • lithium ions are released from the negative electrode 22 and absorbed in the positive electrode 21 through the electrolytic solution with which the separator 23 is impregnated.
  • the nonaqueous electrolyte battery may be designed so that an open circuit voltage at the time of complete charge (that is, the battery voltage) is, for example, within the range of 3.60 V to 6.00 V, preferably 4.20 V to 6.00 V, and more preferably 4.40 V to 6.00 V.
  • an open circuit voltage at the time of complete charge is, for example, set to 4.40 V or more in a battery using layered rock salt type lithium composite oxide or the like as the positive electrode active material
  • the amount of lithium released per unit mass increases as compared with the 4.20 V battery even in the same positive electrode active material, the amounts of the positive electrode active material and the negative electrode active material are adjusted correspondingly to obtain high energy density.
  • the nonaqueous electrolyte battery is produced, for example, by the following procedure.
  • the positive electrode 21 is prepared. First, a positive electrode active material and, as required, a binder and a conductive agent and the like are mixed to form a positive electrode mixture, which is then dispersed in, for example, an organic solvent to prepare a paste or slurry positive electrode mixture slurry.
  • the positive electrode mixture slurry is uniformly applied onto both surfaces of the positive electrode current collector 21A and then dried to form the positive electrode active material layer 21B.
  • the positive electrode active material layer 21B is compression-molded using a roll press machine or the like while heating the positive electrode active material layer 21B as required. In this case, compression molding may be repeated a plurality of times.
  • the negative electrode 22 is prepared by the same procedure as in the positive electrode 21 described above. First, a negative electrode active material and, as required, a binder and a conductive agent or the like are mixed to form a negative electrode mixture, which is then dispersed in, for example, an organic solvent to prepare a paste or slurry negative electrode mixture slurry.
  • the negative electrode mixture slurry is uniformly applied onto both surfaces of the negative electrode current collector 22A and dried to form the negative electrode active material layer 22B, and then the negative electrode active material layer 22B is compression-molded.
  • a nonaqueous electrolyte battery is assembled using the positive electrode 21 and the negative electrode 22.
  • the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like
  • the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like.
  • the positive electrode 21 and the negative electrode 22 are laminated and wound with the separator 23 having the insulating layers formed on both surfaces thereof interposed between the positive electrode and the negative electrode to form the wound electrode body 20, and then a center pin 24 is inserted into the winding center.
  • the wound electrode body 20 is housed inside the battery can 11 while being sandwiched between the pair of insulating plates 12, 13.
  • a tip of the positive electrode lead 25 is attached to the safety valve mechanism 15 by welding or the like
  • a tip of the negative electrode lead 26 is attached to the battery can 11 by welding or the like.
  • an electrolytic solution is filled inside the battery can 11 to impregnate the separator 23 with the electrolytic solution.
  • the battery cover 14, the safety valve mechanism 15, and the positive temperature coefficient element 16 are crimped at the open end of the battery can 11 with a gasket 17 interposed therebetween. Thereby, the nonaqueous electrolyte battery shown in FIG. 1 and FIG. 2 is completed.
  • the nonaqueous electrolyte battery is one in which a wound electrode body 30 is housed inside an outer member 40.
  • a positive electrode lead 31 and a negative electrode lead 32 are attached to the wound electrode body 30.
  • the positive electrode lead 31 and the negative electrode lead 32 are led out from the inside to the outside of the outer member 40 in the same direction.
  • the outer member 40 is a film-like member.
  • the outer member 40 is, for example, a laminated film in which a fusing layer, a metal layer, and a surface protective layer are laminated in this order.
  • the fusing layer is made of, for example, a polyolefin resin such as polyethylene or polypropylene.
  • the metal layer is made of, for example, aluminum or the like.
  • the surface protective layer is made of, for example, nylon or polyethylene terephthalate.
  • the outer member 40 may be a laminated film having another laminate structure or a simple polymer film or a simple metallic film.
  • An adhesive film 41 is interposed between the outer member 40 and the positive electrode lead 31. Similarly, the adhesive film 41 is interposed between the outer member 40 and the negative electrode lead 32.
  • the adhesive film 41 is made of, for example, a material highly adhesive to a metal material.
  • a resin material such as a polyolefin resin is mentioned.
  • the wound electrode body 30 is formed by laminating and winding a positive electrode 33 and a negative electrode 34 with a separator 35 and an electrolyte layer 36 interposed therebetween, and its outermost peripheral portion is protected by a protective tape 37.
  • the wound electrode body 30 may be one in which the separator 35 is omitted.
  • the positive electrode 33 is, for example, one in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A.
  • the configurations of the positive electrode current collector 33A and the positive electrode active material layer 33B are the same as those of the positive electrode current collector 21A and the positive electrode active material layer 21B of the first embodiment, respectively.
  • the negative electrode 34 is, for example, one in which a negative electrode active material layer 34B is provided on both surfaces of a negative electrode current collector 34A.
  • the configurations of the negative electrode current collector 34A and the negative electrode active material layer 34B are the same as those of the negative electrode current collector 22A and the negative electrode active material layer 22B of the first embodiment, respectively.
  • the configuration of the separator 35 is the same as that of the separator 23 of the first embodiment.
  • the electrolyte layer 36 is obtained by holding an electrolytic solution with a polymer compound, and may contain other materials such as various additives as required.
  • the electrolyte layer 36 is, for example, a so-called gel electrolyte.
  • a gel electrolyte is preferred because a high ion conductivity (for example, 1 mS/cm or more at room temperature) can be obtained and leakage of an electrolytic solution can be prevented.
  • polymer compound examples include polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, polycarbonate, a copolymer of vinylidene fluoride and hexafluoropyrene, and the like. These may be used singly or in combination of plural kinds. Among them, polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropyrene are preferred. This is because these are electrochemically stable.
  • the electrolytic solution is the same as in the first embodiment.
  • the solvent of the electrolytic solution is not only a liquid solvent but also a wide concept including a substance having ion conductivity capable of dissociating an electrolyte salt. Therefore, when a polymer compound having ion conductivity is used, the polymer compound is also included in the solvent.
  • the electrolytic solution may be used as it is.
  • the separator 35 is impregnated with the electrolytic solution.
  • the battery of the present technology has an insulating layer similar to that of the first embodiment.
  • the insulating layer is contained in the wound electrode body 30 which is an electrode group, and the insulating layer is formed, for example, between the separator 35 and the positive electrode 33, between the separator 35 and the negative electrode 34, or both of them.
  • the insulating layer may be formed by applying onto at least one side of both surfaces of the separator 35 or by applying onto at least one side of both surfaces of the positive electrode 33 or by applying onto at least one surface of both surfaces of the negative electrode 34.
  • both of the insulating layer and the separator 35 may be referred to as a separator in some cases.
  • the electrolyte layer 36 may be an insulating layer.
  • the electrolyte layer 36 contains insulating particles.
  • the insulating particles the same particles as those described above can be used.
  • an insulating layer does not have to be formed between the separator 35 and the positive electrode 33, and/or the separator 35 and the negative electrode 34.
  • the nonaqueous electrolyte battery is produced by, for example, the following three types of procedures.
  • the positive electrode 33 and the negative electrode 34 are prepared in the same manner as in the first embodiment.
  • An electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
  • a precursor solution containing the electrolytic solution, a polymer compound, and a solvent is prepared, applied onto the positive electrode 33 and the negative electrode 34, and then the solvent is volatilized to form a gel electrolyte layer 36.
  • the electrolyte layer is an insulating layer
  • a precursor solution to which insulating particles are further added is used as the precursor solution.
  • the positive electrode 33 and the negative electrode 34 on which the electrolyte layers 36 are formed, respectively, are laminated and wound with the separator 35 having insulating layers formed on both surfaces thereof interposed between the positive electrode and the negative electrode, and the protective tape 37 is bonded to the outermost peripheral portion of the wound electrodes to prepare a wound electrode body 30.
  • the outer edge portions of the outer member 40 are bonded to each other by thermal fusion bonding or the like to enclose the wound electrode body 30.
  • the adhesive films 41 are inserted between the positive electrode lead 31 and the outer member 40 and between the negative electrode lead 32 and the outer member 40 respectively.
  • the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34.
  • the positive electrode 33 and the negative electrode 34 are laminated and wound with the separator 35 having the insulating layers formed on both surfaces thereof interposed between the positive electrode and the negative electrode, and the protective tape 37 is bonded to the outermost peripheral portion of the wound electrodes to prepare a wound body as a precursor of the wound electrode body 30.
  • the monomer is thermally polymerized into a polymer compound to form a gel electrolyte layer 36. Thereby, the nonaqueous electrolyte battery is completed.
  • a wound body is formed and housed inside a bag-like outer member 40 in the same manner as in the above-described second manufacturing method except for using a separator 35 having polymer compounds and insulating particles applied onto both surfaces thereof.
  • an electrolytic solution is prepared and filled inside the outer member 40, and then the opening of the outer member 40 is sealed by thermal fusion bonding or the like.
  • the outer member 40 is heated while applying a load, and the separator 35 is brought into close contact with the positive electrode 33 and the negative electrode 34 with the polymer compound interposed between the separator and the positive electrode and between the separator and the negative electrode.
  • the polymer compound is impregnated with the electrolytic solution, and the polymer compound gelates to form the electrolyte layer 36 (that is, the insulating layer) containing the insulating particles, thus completing a nonaqueous electrolyte battery.
  • the battery pack is a simplified type battery pack (so-called soft pack) using one secondary battery (unit cell), and is built in an electronic device typified by a smartphone, for example.
  • the battery pack includes a battery cell 111 and a circuit board 116 connected to the battery cell 111.
  • the battery cell 111 is, for example, a laminated film type secondary battery according to the second embodiment.
  • a pair of adhesive tapes 118, 119 are bonded to both side surfaces of the battery cell 111.
  • a protection circuit module (PCM) is formed on the circuit board 116.
  • the circuit board 116 is connected to a positive electrode lead 112 and a negative electrode lead 113 of the battery cell 111 via a pair of tabs 114 and 115 and also connected to a lead 117 with connector for external connection.
  • the circuit board 116 is protected from above and below by a label 120 and an insulating sheet 131. By bonding the label 120, the circuit board 116, the insulating sheet 131 and the like are fixed.
  • the battery pack includes a battery cell 111 corresponding to a power source and a circuit board 116.
  • the circuit board 116 includes, for example, a control part 121, a switch unit 122, a PTC 123, and a temperature detection unit 124. Since the battery cell 111 can be connected to the outside via a positive electrode terminal 125 and a negative electrode terminal 127, the battery cell 111 is charged and discharged via the positive electrode terminal 125 and the negative electrode terminal 127.
  • the temperature detection unit 124 can detect a temperature using a temperature detection terminal (so-called T terminal) 126.
  • the control part 121 controls the operation of the entire battery pack (including the use state of the battery cell 111), and includes, for example, a central processing unit (CPU), a memory, and the like.
  • CPU central processing unit
  • memory volatile and non-volatile memory
  • the control part 121 disconnects the switch unit 122 so that charge current does not flow through the current path of the battery cell 111. Further, for example, when a large current flows during charging, the control part 121 disconnects the switch unit 122 and cuts off the charge current.
  • the control part 121 disconnects the switch unit 122 so that no discharge current flows through the current path of the battery cell 111. Further, for example, when a large current flows during discharging, the control part 121 cuts off the discharge current by disconnecting the switch unit 122.
  • An example of the overcharge detection voltage of the secondary battery is 4.20 V ⁇ 0.05 V or the like.
  • An example of the overdischarge detection voltage is 2.4 V ⁇ 0.1 V or the like.
  • the switch unit 122 switches the use state (availability of connection between the battery cell 111 and the external device) of the battery cell 111 according to an instruction from the control part 121.
  • the switch unit 122 includes, for example, a charge control switch and a discharge control switch.
  • the charge control switch and the discharge control switch are, for example, semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor.
  • MOSFET field effect transistor
  • the temperature detection unit 124 measures the temperature of the battery cell 111 and outputs the measurement result to the control part 121, and includes, for example, a temperature detection element such as a thermistor.
  • the measurement result by the temperature detection unit 124 is used when the control part 121 performs charge-discharge control at the time of abnormal heat generation, or when the control part 121 performs correction processing in calculating a remaining capacity, or the like.
  • circuit board 116 does not have to include the PTC 123.
  • a separate PTC element may be attached to the circuit board 116.
  • An electronic device 300 includes an electronic circuit 301 of the electronic device main body and a battery pack 200.
  • the battery pack 200 is electrically connected to the electronic circuit 301 via a positive electrode terminal 231a and a negative electrode terminal 231b.
  • the electronic device 300 has a configuration which allows the user to detachably attach the battery pack 200.
  • the configuration of the electronic device 300 is not limited to the above configuration, and the electronic device 300 may have a configuration in which the battery pack 200 is incorporated in the electronic device 300 so that the user cannot remove the battery pack 200 from the electronic device 300.
  • the positive electrode terminal 231a and the negative electrode terminal 231b of the battery pack 200 are connected to a positive electrode terminal and a negative electrode terminal of a charger (not shown), respectively.
  • the positive electrode terminal 231a and the negative electrode terminal 231b of the battery pack 200 are connected to a positive electrode terminal and a negative electrode terminal of the electronic circuit 301, respectively.
  • Examples of the electronic device 300 include, but are not limited to, a notebook-sized personal computer, a tablet computer, a mobile phone (smart phone, etc.), personal digital assistants (PDA), display devices (LCD, EL display, electronic paper, head mounted display (HMD), etc.), imaging devices (digital still camera, digital video camera, etc.), audio instruments (potable audio player, etc.), a game machine, a cordless phone handset, an electronic book, an electronic dictionary, a radio, a headphone, a navigation system, a memory card, a pace maker, a hearing aid, an electric power tool, an electric shaver, a refrigerator, an air conditioner, a television set, a stereo, a water heater, a microwave oven, a dishwashing machine, a washing machine, a drier, lighting equipment, a toy, a medical device, a robot, a load conditioner, a traffic light, and the like.
  • PDA personal digital assistants
  • LCD liquid crystal display
  • EL display electronic
  • the electronic circuit 301 includes, for example, a CPU, a peripheral logic part, an interface part, a storage part, and the like, and controls the entire of the electronic device 300.
  • the battery pack 200 is a battery pack of an assembled battery which includes an assembled battery 201 and a charge-discharge circuit 202.
  • the assembled battery 201 is configured by connecting a plurality of secondary batteries 201a in series and/or in parallel.
  • the plurality of secondary batteries 201a are connected, for example, such that n batteries are connected in parallel and m batteries are connected in series (n and m are positive integers).
  • FIG. 7 shows an example in which six secondary batteries 201a are connected with two batteries in parallel and three batteries in series (2P3S).
  • the secondary battery 201a the battery according to the first embodiment is used.
  • the charge-discharge circuit 202 controls charge to the assembled battery 201.
  • the charge-discharge circuit 202 controls discharge to the electronic device 300.
  • the battery according to the first embodiment or the second embodiment, or the battery pack of the unit cell according to the third embodiment may be used.
  • the electric storage system may be any system as long as it uses electric power and includes merely an electric power device.
  • the electric power system includes, for example, a smart grid, a household energy management system (HEMS), a vehicle, and the like, and can also store electricity.
  • HEMS household energy management system
  • the electric storage device (electric storage module) is applied to, for example, power sources for electric power storage for buildings including houses or power generation facilities.
  • an electric storage module including a battery block in which a plurality of batteries are connected in at least one of a parallel manner and a series manner, and a control part for controlling charging and discharging of these battery blocks, is mentioned.
  • An example of the configuration of the electric storage device is, for example, a plurality of battery blocks housed in an outer case.
  • the battery according to the first embodiment can be used.
  • the electric storage system examples include, for example, the following first to fifth electric storage systems and the like.
  • the first electric storage system is an electric storage system in which the electric storage device is charged by a power generation device that generates power from renewable energy.
  • the second electric storage system is an electric storage system which has an electric storage device and supplies power to an electronic device connected to the electric storage device.
  • the third electric storage system is an electric storage system including electronic devices which receive power supply from the electric storage device.
  • the fourth electric storage system is an electric power system including an electric power information transmitting and receiving unit which transmits and receives signals to and from another device via a network, and performing charge-discharge control of the above-mentioned electric storage device based on information received by the transmitting and receiving unit.
  • the fifth electric storage system is an electric power system which receives power supply from the above-mentioned electric storage device or supplies electric power from the power generation device or the power network to the electric storage device.
  • the electric storage system 400 is an electric storage system for residential use, and electric power is supplied from a centralized electric power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydraulic power generation 402c to the electric storage device 403 via a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like. With this, electric power is supplied from an independent power source such as domestic power generation device 404 to the electric storage device 403. The electric power supplied to the electric storage device 403 is stored. Electric power to be used in a house 401 is supplied by way of the electric storage device 403. A similar electric storage system can be used not only for the house 401 but also for a building.
  • the domestic power generation device 404 In the house 401, the domestic power generation device 404, power consumption equipment 405, the electric storage device 403, a control device 410 that controls each equipment, the smart meter 407, the power hub 408, and sensors 411 that acquire various kinds of information are provided.
  • the respective pieces of equipment are connected by the power network 409 and the information network 412.
  • a solar cell, a fuel cell, or the like is used as the domestic power generation device 404, and the generated electric power is supplied to the power consumption equipment 405 and/or the electric storage device 403.
  • the power consumption equipment 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d or the like.
  • the power consumption equipment 405 includes an electric vehicle 406.
  • the electric vehicle 406 is an electric automobile 406a, a hybrid car 406b, an electric motorbicycle 406c or the like.
  • the electric storage device 403 includes one or more batteries according to the first embodiment or the second embodiment.
  • the smart meter 407 has a function of measuring the use amount of commercial power and sending the use amount measured to an electric power company.
  • the power network 409 may be any one or combination of DC (direct current) power supply, AC (alternate current) power supply, and non-contact power supply.
  • the various sensors 411 are, for example, a human sensor, an illuminance sensor, an object detection sensor, a power consumption sensor, a vibration sensor, a contact sensor, a temperature sensor, an infrared sensor, and the like. Information acquired by the various sensors 411 is transmitted to the control device 410. Based on the information from the sensors 411, the state of weather, the state of person, and the like are grasped and the power consumption equipment 405 is automatically controlled to allow minimization of the energy consumption. Further, the control device 410 can transmit information relating to the house 401 to an external electric power company or the like via an Internet.
  • Branching of the power line and processing of DC-AC conversion, and the like are carried out by the power hub 408.
  • a communication system of the information network 412 connected to the control device 410 there are a method of using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver: transmitting/receiving circuit for asynchronous serial communication) and a method of utilizing a sensor network based on a wireless communication standard such as Bluetooth (registered trade mark), ZigBee or Wi-Fi.
  • Bluetooth (registered trademark) system is applied to multimedia communication and allows communication of a one-to-many connection.
  • ZigBee is a standard using a physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4.
  • IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
  • the control device 410 is connected to an external server 413.
  • the server 413 may be managed by any of the house 401, an electric power company, and a service provider.
  • the information transmitted and received by the server 413 is, for example, power consumption information, life pattern information, electric power bill, weather information, natural disaster information, and information relating to power trading.
  • These pieces of information may be transmitted and received from power consumption device (for example, a television receiver) in the home, or may be transmitted and received from a device outside the home (for example, mobile phone, etc.).
  • These pieces of information may be displayed on a device having a display function, for example, a television receiver, a cellular phone, a PDA, or the like.
  • the control device 410 which controls each unit is composed of a CPU, a RAM, a ROM, and the like, and in this example, the control device 410 is stored in the electric storage device 403.
  • the control device 410 is connected to the electric storage device 403, the domestic power generation device 404, the power consumption equipment 405, the various sensors 411, and the server 413 via the information network 412, and has, for example, a function of adjusting the use amount of commercial power and the amount of power generation.
  • the control device 410 may have a function of carrying out power trading in a power market and the like.
  • control device 410 may be stored in the smart meter 407 or may be configured singly. Further, the electric storage system 400 may be used for a plurality of homes in a collective housing, or may be used for a plurality of single-family houses.
  • an electric vehicle including the battery according to the first embodiment or the second embodiment will be described.
  • Examples of electric vehicles include railroad vehicles, golf carts, electric carts, electric automobiles (including hybrid automobile), agricultural work vehicles (tractors, combines, etc.), and the like.
  • An example of an electric automobile will be described below.
  • This hybrid vehicle 500 is a hybrid vehicle employing a series hybrid system.
  • the series hybrid system is a car that runs with an electric power driving force converting device 503 by using electric power generated by an electric generator activated through an engine or electric power once stored in a battery.
  • an engine 501 an electric generator 502, the electric power driving force converting device 503, a driving wheel 504a, a driving wheel 504b, a wheel 505a, a wheel 505b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511 are mounted.
  • the battery 508 the battery according to the first embodiment or the second embodiment is used.
  • the hybrid vehicle 500 runs by using the electric power driving force converting device 503 as a power source.
  • the electric power driving force converting device 503 is a motor.
  • the electric power driving force converting device 503 is operated by the electric power of the battery 508 and a rotational force of the electric power driving force converting device 503 is transmitted to the driving wheels 504a and 504b.
  • DC-AC direct current-alternating current
  • AC-DC conversion AC-DC conversion
  • the various sensors 510 control the engine rotational speed via the vehicle control device 509 and control the opening degree of a throttle valve that is not shown in the diagram (throttle opening).
  • the various sensors 510 include a velocity sensor, an acceleration sensor, an engine rotational speed sensor, or the like.
  • the rotational force of the engine 501 is transmitted to the electric generator 502, and the electric power generated by the electric generator 502 through the rotational force can be accumulated in the battery 508.
  • the battery 508 is connected to a power source outside the hybrid vehicle 500 through the charging port 511 to thereby receive supply of electric power from the external power source by using the charging port 511 as an input port and to accumulate the received electric power.
  • the hybrid vehicle 500 may include an information processing device which executes information processing relating to vehicle control based on information concerning the battery.
  • an information processing device for example, there is an information processing device for displaying the battery remaining capacity based on information concerning the remaining capacity of the battery, or the like.
  • the above is an example of the series hybrid car which runs with a motor by using electric power generated by an electric generator activated through an engine or electric power once stored in a battery.
  • the present technology can be effectively applied also to a parallel hybrid car which employs both outputs of engine and motor as the drive source and uses, with appropriate switching, three systems, running by only the engine, running by only the motor, and running by the engine and the motor.
  • the present technology can be effectively applied also to a so-called electric vehicle which does not use an engine and runs by driving by only a drive motor.
  • Ch A to Ch N in the following description are as follows.
  • Ch A Compound represented by a formula (2-1)
  • Ch B Compound represented by a formula (1-1)
  • Ch C Compound represented by a formula (1-2)
  • Ch D Compound represented by a formula (1-3)
  • Ch E Compound represented by a formula (1-4)
  • Ch F Compound represented by a formula (2-2)
  • Ch G Compound represented by a formula (2-3)
  • Ch H Compound represented by a formula (2-4)
  • Ch I Compound represented by ae formula (2-5)
  • Ch J Compound represented by a formula (1-5)
  • Ch K Compound represented by a formula (2-6)
  • Ch L Compound represented by a formula (2-7)
  • Ch M Compound represented by a formula (2-8)
  • Ch N Compound represented by a formula (3)
  • Lithium carbonate (Li 2 CO 3 ) and cobalt carbonate (CoCO 3 ) were mixed in a molar ratio of 0.5 : 1 and then calcined at 900°C for 5 hours in air to obtain lithium cobalt composite oxide (LiCoO 2 ).
  • a positive electrode mixture was formed by mixing 91 parts by mass of lithium cobalt composite oxide as a positive electrode active material, 6 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder, and then a paste-like positive electrode mixture slurry was prepared by dispersing N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode mixture slurry was applied onto both sides of a positive electrode current collector made of a belt-like aluminum foil (12 ⁇ m in thickness), and dried. Then, compression molding was performed by a roll-press machine to form a positive electrode active material layer. Thereafter, a positive electrode lead made of aluminum was attached to one end of the positive electrode current collector by welding.
  • this negative electrode mixture slurry was uniformly applied onto both surfaces of a negative electrode current collector made of a belt-like copper foil having a thickness of 15 ⁇ m, dried, and compression molded to form a negative electrode active material layer.
  • the amount of the positive electrode active material and the amount of the negative electrode active material were adjusted so that the open circuit voltage at the time of complete charge (that is, the battery voltage) was the voltage value shown in Table 1.
  • separator As a separator, a separator with a heat-resistant insulating layer in which insulating layers were formed on both sides of the following separator was used.
  • a microporous polyethylene separator having a thickness of 12 ⁇ m was immersed in a polyvinylidene fluoride solution having alumina particles dispersed therein, then N-methyl-2-pyrrolidone was removed with water, and then the separator was dried with hot air at 80°C.
  • an insulating layer with a thickness of 5 ⁇ m in total of both surfaces was formed on both surfaces of the microporous polyethylene separator to prepare a separator with a heat-resistant insulating layer.
  • the electrolytic solution was prepared by dissolving 1.2 mol/kg of LiPF 6 as an electrolyte salt in a mixture composed of propylene carbonate and ethylmethyl carbonate in proportions of 5 : 95 (mass ratio) as a solvent, and adding Ch B as an additive in an amount of 1% by mass with respect to the whole electrolytic solution.
  • a positive electrode, a separator with a heat-resistant insulating layer, and a negative electrode were laminated to form a laminate, and the laminate was wound in the longitudinal direction to obtain an electrode wound body.
  • the electrode wound body was sandwiched by an outer package film formed by sandwiching an aluminum foil between a pair of resin films, and the outer peripheral edge portion was thermally fused leaving one direction for filling of the electrolytic solution. After that, the electrolytic solution was filled in the outer package film, a remaining outer peripheral edge portion of the outer package film was thermally fused under a reduced pressure and sealed, and the electrode wound body was hermetically sealed in the outer package film. At this time, a portion to which the resin piece of the positive electrode terminal and the negative electrode terminal was applied was tucked into the sealing portion of the outer package film. In this way, a battery (laminated film type battery) was completed.
  • a battery was prepared in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution was changed as shown in Table 1.
  • a battery was prepared in the same manner as in Example 1-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 1.
  • a microporous polyethylene separator having a thickness of 12 ⁇ m was used in place of the separator with a heat-resistant insulating layer.
  • charge-discharge of three cycles were carried out at 30°C.
  • charge-discharge up to the third cycle charge was performed until the battery voltage reached a predetermined voltage (charging voltage shown in Table 1) at a constant current density of 1 mA/cm 2 and charge was performed until the current density reached 0.02 mA/cm 2 at a constant voltage of the predetermined voltage, and then the battery was charged at a constant current density of 1 mA/cm 2 until the battery voltage reached a predetermined voltage (2.5 V).
  • the charge-discharge of fourth cycle was performed in which the battery was charged at a constant current density of 1 mA/cm 2 at 50°C until the battery voltage reached a predetermined voltage (charge voltage shown in Table 1), and charged until the current density reached 0.02 mA/cm 2 at a constant voltage of the predetermined voltage, and then the battery was discharged at 50°C. At this time, discharge was carried out at a constant current density of 1 mA/cm 2 at 50°C until the battery voltage reached a predetermined voltage (2.5 V). 100 cycles of charge-discharge were carried out under the same charge-discharge conditions, and the discharge capacity retention ratio (%) at the 104th cycle was obtained when the discharge capacity at the fourth cycle was taken as 100.
  • Example 1 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC DMC Propyl Propionate Ethyl Propionate ⁇ -butyrolactone Type Amount [% by mass]
  • Example 1-1 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC DMC Propyl Propionate Ethyl Propionate ⁇ -butyrolactone Type Amount [% by mass]
  • Example 1-1 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC DMC Propyl Propionate Ethyl Propionate ⁇ -butyrolactone Type Amount [% by mass]
  • Example 1-1 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Re
  • the numerical value of the item of the composition of the solvent of the electrolytic solution is the mass percentage [mass%] with respect to the total mass of the nonaqueous solvent (this also applies to the following Tables 2 to 10).
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and the Ch B as an additive.
  • a battery was prepared in the same manner as in Example 1-18 except that the type and amount of the additive were changed as shown in Table 2.
  • a battery was prepared in the same manner as in Example 2-1 except that the type and amount of the additive were changed as described in Table 2.
  • Example 1-18 the cycle characteristics were evaluated in the same manner as in Example 1-1. The results are shown in Table 2. The measurement results of Example 1-18, Comparative Example 1-9 to Comparative Example 1-10, and Comparative Example 1-20 to Comparative Example 1-22 are also shown in Table 2.
  • Example 2 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC Type Amount [% by mass]
  • Example 2-1 Present 37.5 37.5 25 Ch A 0.01 52
  • Example 2-2 Present 0.1 57
  • Example 2-3 Present 1 61
  • Example 2-4 Present 3 61
  • Example 2-5 Present 5
  • Example 2-6 Present 37.5 37.5 25 Ch B 0.01
  • Example 2-7 Present 0.1 70
  • Example 1-18 Present 1
  • Example 2-8 Present 3 71
  • Example 2-9 Present 5 67
  • Example 2-10 Present 37.5 37.5 25 Ch C 0.01 59
  • Example 2-11 Present 0.1 65
  • Example 2-12 Present 1
  • Example 2-13 Present 3 68
  • Example 2-14 Present 5 63
  • Example 2-15 Present 37.5 37.5 25 Ch D 0.01
  • Example 2-16 Present 0.1 62
  • Example 2-17 Present 1
  • Example 2-19 Present 5 61
  • Example 2-20 Present 37.5 37.5 25 Ch F 0.
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch D and Ch F to Ch M as an additive.
  • the amount of the additive was 0.1% by mass or more and 3% by mass or less, more excellent effects could be achieved.
  • a battery was prepared in the same manner as in Example 2-3 except that the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 3.
  • Example 3 Charge Voltage [V] Composition of Solvent of Electrolytic Solution Additive Other Additive Discharge Capacity Retention Ratio [%] Type Amount [% by mass] Type Amount [% by mass] Example 2-3 Ch A 1 None - 61
  • Example 3-1 Succinonitrile 1 58
  • Example 3-2 Adiponitrile 1 60
  • Example 3-3 1,3-propane sultone 1
  • Example 3-4 2-propynyl methanesulfonate 1
  • Example 3-5 1,3-dioxane 1 61
  • Example 3-6 LiBF 4 1 62
  • Example 3-7 LiBOB 1 62
  • Example 3-8 LiTFSA 1 62
  • Example 3-9 Lithium difluorophosphate 1 61
  • Example 1-18 Ch B None - 72
  • Example 3-9 Succinonon
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A, Ch B, Ch D, Ch F, and Ch G as an additive.
  • a battery was prepared in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution, the type and amount of the additive, and the charge voltage were changed as shown in Table 4.
  • a battery was prepared in the same manner as in Example 4-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 4.
  • Example 4 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The results are shown in Table 4. The predetermined voltage at the time of charging is the voltage value shown in Table 4.
  • Table 4 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC Type Amount [% by mass]
  • Example 4-1 Present Ch A 0.01 77
  • Example 4-2 Present 0.1 82
  • Example 4-3 Present 1 87
  • Example 4-4 Present 3
  • Example 4-4 Present 3
  • Example 4-4 Present 5
  • Example 4-4 Present 5
  • Example 4-4 Present Ch B 0.01 85
  • Example 4-7 Present 0.1 94
  • Example 4-8 Present 1 96
  • Example 4-9 Present 3 97
  • Example 4-10 Present 5 91
  • Example 4-11 Present Ch C 0.01 82
  • Example 4-12 Present 0.1 92
  • Example 4-13 Present 1 95
  • Example 4-14 Present 3 95
  • Example 4-15 Present 5 90
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch D and Ch F to Ch M as an additive.
  • a positive electrode and a negative electrode were prepared in the same manner as in Example 1-1.
  • a gel electrolyte layer containing alumina particles as ceramic particles of an insulating material was formed as an insulating layer on the prepared positive electrode and negative electrode.
  • a gel electrolyte layer In order to form a gel electrolyte layer, first, polyvinylidene fluoride in which hexafluoropropylene is copolymerized in a ratio of 6.9 mass%, alumina particle powder having an average particle diameter of 0.3 ⁇ m, a nonaqueous electrolytic solution, and dimethyl carbonate are mixed, and the resulting mixture was stirred and dissolved to obtain a sol electrolyte solution.
  • the obtained sol electrolyte solution was uniformly applied onto both surfaces of the positive electrode and the negative electrode. Thereafter, the electrolyte solution was dried to remove dimethyl carbonate. In this way, a gel electrolyte layer was formed on both surfaces of the positive electrode and the negative electrode.
  • the laminate was wound in the longitudinal direction to obtain an electrode wound body.
  • the electrode wound body was sandwiched by an outer package film formed by sandwiching an aluminum foil between a pair of resin films, the outer peripheral edge portion of the outer package film was thermally fused under a reduced pressure and sealed, and the electrode wound body was hermetically sealed in the outer package film. At this time, a portion to which the resin piece of the positive electrode terminal and the negative electrode terminal was applied was tucked into the sealing portion of the outer package film. In this way, a gel electrolyte battery was completed.
  • a battery was prepared in the same manner as in Example 5-1 except that the composition of the solvent of the electrolytic solution, and the kind and amount of the additive were changed as shown in Table 5.
  • a battery was prepared in the same manner as in Example 5-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 5.
  • Example 5 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The measurement results are shown in Table 5. The predetermined voltage at the time of charging is a voltage value shown in Table 5.
  • Table 5 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC Type Amount [% by mass]
  • Example 5-1 Present Ch A 0.01 48
  • Example 5-2 Present 0.1 55
  • Example 5-3 Present 1 57
  • Example 5-4 Present 3 57
  • Example 5-5 54
  • Example 5-6 Present Ch B 0.01 59
  • Example 5-7 Present 0.1 66
  • Example 5-8 Present 1 68
  • Example 5-9 Present 3 67
  • Example 5-10 Present 5 60
  • Example 5-11 Present Ch D 0.01 52
  • Example 5-12 Present 0.1 59
  • Example 5-13 4.4 Present 50 50 1 62
  • Example 5-14 Present 3 62
  • Example 5-15 Present 5 58
  • Example 5-16 Present Ch F 0.01 50
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch B, Ch D and Ch F to Ch G as an additive.
  • the following negative electrode using silicon as a negative electrode active material was prepared.
  • the amount of the positive electrode active material and the amount of the negative electrode active material were adjusted so that the charging voltage was 4.35 V.
  • a battery was prepared in the same manner as in Example 1-1 except for the above.
  • Silicon powder having an average particle size of 5 ⁇ m was used as a negative electrode active material, and 90 parts by mass of the silicon powder, 5 parts by mass of the graphite powder, and 5 parts by mass of a polyimide precursor as a binder were mixed, and N-methyl-2-pyrrolidone was added to prepare a slurry.
  • the resulting negative electrode mixture slurry was uniformly applied to both surfaces of a negative electrode current collector 22A made of a belt-like copper foil having a thickness of 15 ⁇ m, dried, compression molded, and heated at 400°C for 12 hours in a vacuum atmosphere to form a negative electrode active material layer 22B.
  • a battery was prepared in the same manner as in Example 6-1 except that the composition of the solvent of the electrolytic solution, and the type and the amount of the additive were changed as shown in Table 6.
  • a battery was prepared in the same manner as in Example 6-1 except that the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 6.
  • Example 6 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The measurement results are shown in Table 6. The predetermined voltage at the time of charging is a voltage value shown in Table 6.
  • Table 6 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Amount [% by mass] Discharge Capacity Retention Ratio [%] EC PC EMC
  • Example 6-1 Present Ch A 0.01 34
  • Example 6-2 Present 0.1 46
  • Example 6-3 Present 1 50
  • Example 6-4 Present 3 49
  • Example 6-5 Present 5 44
  • Example 6-6 Present Ch B 0.01 40
  • Example 6-7 Present 0.1 59
  • Example 6-8 Present 1 62
  • Example 6-9 Present 3 61
  • Example 6-10 Present 5 58
  • Example 6-11 Present Ch D 0.01 38
  • Example 6-12 Present 0.1 55
  • Example 6-13 4.35
  • Example 6-14 Present 3 58
  • Example 6-15 Present 5 53
  • Example 6-16 Present Ch F 0.01
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch B, Ch D and Ch F to Ch G as an additive.
  • a battery was prepared in the same manner as in Example 1-1 except for the above.
  • the mixture was dispersed in water, and sodium hydroxide (NaOH) was added thereto while adequately stirring to obtain a manganese • nickel • cobalt • aluminum composite coprecipitated hydroxide.
  • the coprecipitate was washed with water and dried, and then lithium hydroxide monohydrate was added to obtain a precursor.
  • the precursor was calcined at 800°C for 10 hours in the air to obtain the intended positive electrode active material.
  • a battery was prepared in the same manner as in Example 7-1 except that the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 7.
  • a battery was prepared in the same manner as in Example 7-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 7.
  • Example 7 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The measurement results are shown in Table 7. The predetermined voltage at the time of charging is a voltage value shown in Table 7. [Table 7] Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC EMC Type Amount [% by mass] Example 7-1 Present Ch A 0.01 42 Example 7-2 Present 0.1 50 Example 7-3 Present 1 53 Example 7-4 Present 3 53 Example 7-5 Present 5 47 Example 7-6 Present Ch B 0.01 50 Example 7-7 Present 0.1 63 Example 7-8 Present 1 65 Example 7-9 Present 3 66 Example 7-10 Present 5 62 Example 7-11 Present Ch D 0.01 47 Example 7-12 Present 0.1 57 Example 7-13 4.6 Present 25 25 50 1 59 Example 7-14 Present 3 60 Example 7-15 Present 5 56 Example 7-16 Present Ch F 0.01 45 Example 7-17 Present 0.1 54 Example 7-18 Present 1 56 Example 7-19 Present 3 56 Example 7-20 Present 5 53 Example 7-21 Present Ch G 0.01 42
  • a battery was prepared in the same manner as in Example 1-1 except for the above.
  • Lithium carbonate (Li 2 CO 3 ), manganese oxide (MnO 2 ), and nickel oxide (NiO) were weighed so as to have a predetermined molar ratio, and then mixed using a ball mill. Subsequently, the resulting mixture was calcined at 800°C for 10 hours in air, and then cooled. Subsequently, the mixture was re-mixed using a ball mill and then calcined at 700°C for 10 hours in the air to obtain a lithium nickel manganese composite oxide (LiNi 0.5 Mn 1.5 O 4 ) as a target positive electrode active material.
  • a battery was prepared in the same manner as in Example 8-1 except that the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 8.
  • a battery was prepared in the same manner as in Example 8-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 8.
  • Example 8-18 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The measurement results are shown in Table 8. The predetermined voltage at the time of charging is a voltage value shown in Table 8.
  • Table 8 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC DEC Type Amount [% by mass]
  • Example 8-1 Present Ch A 0.01 41
  • Example 8-2 Present 0.1 51
  • Example 8-3 Present 1
  • Example 8-4 Present 3
  • Example 8-5 Present 5
  • Example 8-6 Present Ch B 0.01 48
  • Example 8-7 Present 0.1 60
  • Example 8-8 Present 1 63
  • Example 8-9 Present 3 64
  • Example 8-10 Present 5 58
  • Example 8-11 Present Ch D 0.01 45
  • Example 8-12 Present 0.1 56
  • Example 8-13 4.95 Present 25 25 50 1 60
  • Example 8-14 Present 3 60
  • Example 8-15 Present 5
  • Example 8-16 Present Ch F 0.01 44
  • Example 8-17 Present 0.1
  • the high-temperature cycle characteristics could be improved by having an insulating layer and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch B, Ch D and Ch F to Ch G as an additive.
  • a positive electrode and an insulating layer were prepared as follows. A microporous polyethylene separator not having an insulating layer and having a thickness of 12 ⁇ m was used in place of the separator with a heat-resistant insulating layer. A battery was prepared in the same manner as in Example 1-1 except for the above.
  • a positive electrode was prepared in the same manner as in Example 1-1. 80 parts by mass of alumina particle powder as ceramic particles and 20 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed and the resulting mixture was diluted with N-methyl-2-pyrrolidone solvent to prepare a mixed liquid. The positive electrode was immersed in the mixed liquid, and a film thickness was controlled with a gravure roller, and then the solvent was removed by passing the positive electrode through a dryer in an atmosphere of 120°C to prepare a positive electrode 22 on which a porous film (insulating layer) with a thickness of 5 ⁇ m was formed. Thereafter, a positive electrode lead was attached to one end of the positive electrode current collector.
  • PVdF polyvinylidene fluoride
  • a battery was prepared in the same manner as in Example 9-1 except that the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 9
  • a battery was prepared in the same manner as in Example 9-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 9.
  • Example 9-1 Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC DEC Type Amount [% by mass]
  • Example 9-1 4.4 Present - 25 75 Ch A 0.1 45
  • Example 9-2 Present - 1 50
  • Example 9-3 Present - 5 44
  • Example 9-4 Present - Ch B 0.1 59
  • Example 9-5 Present - 1 62
  • Example 9-6 Present - 5 54
  • Example 9-7 Present - Ch D 0.1 55
  • Example 9-8 Present - 1 56
  • Example 9-9 Present - 5 52 Example 9-10 Present - Ch E 0.1 47
  • Example 9-11 Present - 1 52
  • Example 9-12 Present - 5 46
  • Comparative Example 1-2 4.4 Present - 25 75 None - 37
  • Comparative Example 9-1 Present - 25 75 Ch N 1 41
  • Comparative Example 9-2 Present 25 75 None - 42
  • Comparative Example 9-3 Present 25 75 Ch B 1 44 Comparative Example 9-4 None
  • the high-temperature cycle characteristics could be improved by having an insulating layer formed on the positive electrode and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch E as an additive.
  • a negative electrode and an insulating layer were prepared as follows. A microporous polyethylene separator not having an insulating layer and having a thickness of 12 ⁇ m was used in place of the separator with a heat-resistant insulating layer. A battery was prepared in the same manner as in Example 1-1 except for the above.
  • a negative electrode was prepared in the same manner as in Example 1-1. 80 parts by mass of alumina particle powder as ceramic particles and 20 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed and the resulting mixture was diluted with N-methyl-2-pyrrolidone solvent to prepare a mixed liquid. The negative electrode was immersed in the mixed liquid, and a film thickness was controlled with a gravure roller, and then the solvent was removed by passing a positive electrode plate through a dryer in an atmosphere of 120°C to prepare a negative electrode on which a porous film (insulating layer) with a thickness of 5 ⁇ m was formed. Thereafter, a negative electrode lead made of nickel was attached to one end of the negative electrode current collector.
  • PVdF polyvinylidene fluoride
  • a battery was prepared in the same manner as in Example 10-1 except that the composition of the solvent of the electrolytic solution, and the type and amount of the additive were changed as shown in Table 10.
  • a battery was prepared in the same manner as in Example 10-1 except that at least one of the presence or absence of formation of the insulating layer, the composition of the solvent of the electrolytic solution, and the type and amount of the additive was changed as shown in Table 10.
  • Example 10 For the prepared batteries, the cycle characteristics were evaluated in the same manner as in Example 1-1. The measurement results are shown in Table 10. The measurement results of Comparative Example 1-3, Comparative Example 1-5, and Comparative Example 1-11 are also shown in Table 10. [Table 10] Charge Voltage [V] Insulating Layer Composition of Solvent of Electrolytic Solution Additive Discharge Capacity Retention Ratio [%] EC PC DEC Type Amount [% by mass] Example 10-1 4.4 Present - 50 50 Ch A 0.1 53 Example 10-2 Present - 1 55 Example 10-3 Present - 5 51 Example 10-4 Present - Ch B 0.1 57 Example 10-5 Present - 1 60 Example 10-6 Present - 5 56 Example 10-7 Present - Ch D 0.1 55 Example 10-8 Present - 1 59 Example 10-9 Present - 5 54 Example 10-10 Present - Ch E 0.1 54 Example 10-11 Present - 1 57 Example 10-12 Present - 5 52 Comparative Example 1-3 4.4 Present - 50 50 None - 28 Comparative Example 10-1 Present - 50 50 Ch N 1 41
  • the high-temperature cycle characteristics could be improved by having an insulating layer formed on the positive electrode and by using the electrolytic solution which contains the nonaqueous solvent containing propylene carbonate in an amount of 5% by mass or more, and any one of Ch A to Ch E as an additive.
  • the battery according to the present technology can be similarly applied to a case having another battery structure such as a prismatic shape.
  • a laminated electrode body may be used in place of the wound electrode body.
  • the battery according to the present technology can also be applied to, for example, a flexible battery mounted on a wearable terminal such as smart watch, head mounted display, iGlass (registered trademark) or the like.
  • the battery according to the present technology can also be applied to a battery mounted on an aircraft, a flying object such as an unmanned aerial vehicle, or the like.
  • the present technology can adopt the following configuration.

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EP16853223.2A 2015-10-08 2016-08-23 Batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage de puissance et système de puissance Pending EP3352282A4 (fr)

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